Polymerizable monomer, polymer thereof and process for preparing same

ABSTRACT

The present invention provides a polymerizable monomer represented by the general formula (1), polymer thereof, process for preparing the polymer and the use of the polymer ##STR1## wherein R 1  is a hydrogen atom, methyl, chlorine or cyano, R 2  is alkylene having 1 to 4 carbon atoms, R 3  is alkylene having 3 to 10 carbon atoms, R 4  is alkyl having 6 to 18 carbon atoms, R 6  to R 8  are the same or different and are each alkyl or substituted alkyl having 1 to 3 carbon atoms, A is methylene, phenylene, substituted phenylene, --CH 2  O--, --CH 2  CH 2  O--, --CO--, --CO--N(R 9 )-- (wherein R 9  is a hydrogen atom or methyl) or vinylene, m is 0 or 1, and X and Y are the same or different, and are each a monovalent anion or form a bivalent anion when taken together.

TECHNICAL FIELD

The present invention relates to polymerizable monomer, polymersthereof, process for preparing the polymer and the use of the polymer.The invention provides polymerizable monomers for readily givingantibacterial polymers which are excellent in bactericidal activity,high in safety and stability and capable of retaining their effect overa prolonged period of time, and also provides these polymers, processfor preparing the same and the use of the same.

The antibacterial polymers derived from the polymerizable monomers ofthe invention are usable, for example, for sterilization or slimecontrol of tap water, cooling water and water in pools, for compositionsfor preventing soiling of fishing nets, ship bottoms, underwaterstructures, etc., for food packaging materials, building materials,agricultural materials, medical articles, materials or utensils for usein the oral cavity (toothbrushes, toothpastes, etc.), spectacle frames,cosmetics, clothes, household utensils and the like, and a wide varietyof other uses.

BACKGROUND ART

Among the conventional antibacterial compounds, those of low molecularweight are used as merely mixed with materials (such as resins) forforming various products, so that the antibacterial compound inevitablydissolves out, consequently becoming impaired in antibacterial activityand causing environmental pollution. Also encountered are problems suchas toxicity of the compound to the living body due to contact with theproduct, and appearance of resistant bacteria.

To solve these problems, antibacterial polymers have been developed inrecent years which are prepared by introducing an antibacterialfunctional group into high-molecular-weight compounds. Theseantibacterial polymers include, for example, those comprising arepeating unit represented by the general formula (3) (JP-A-100254/1986)and those comprising a repeating unit represented by the general formula(4) (JP-A-246205/1986). ##STR2## wherein R¹⁰ is methyl or ethyl, R¹¹ isalkyl having 3 to 30 carbon atoms. ##STR3## wherein the groups R¹² arethe same or different and are each alkyl having 1 to 4 carbon atoms, R¹³is alkyl having 14 to 20 carbon atoms, and X⁻ is an anion.

However, these known antibacterial polymers are not fully satisfactoryin antibacterial activity.

The antibacterial polymer is prepared by reacting a tertiary amine witha polymer having a reactive chlorine group in its side chain tosubstitute the tertiary amine for the reactive chlorine group, whereasdifficulty is encountered in completely effecting the substitution,consequently permitting many active chlorine-containing functionalgroups to remain in the molecule. Accordingly, the antibacterial polymeritself problems in respect of stability and safety to the human body.

To overcome these problems, antibacterial polymers are also prepared bysynthesizing an antibacterial polymerizable monomer and copolymerizingthe monomer with other monomer. For example, antisoiling coatingcompositions are known which comprise as an effective component acopolymer containing a monomer represented by the general formula (5)(JP-A-64167/1990). ##STR4## wherein R¹⁴ is a straight-chain or branchedalkyl or alkenyl having 8 to 22 carbon atoms, R¹⁵ and R¹⁶ are each alkylhaving 1 to 3 carbon atoms, R¹⁷ is a hydrogen atom or methyl, B is O--COor O--CH₂, and X is a monovalent anion.

Further according to a report of Senuma et al., polymers are prepared byreacting chloromethylstyrene with cetyldimethylamine [C₁₆ H₃₃ N(CH₃)₂ ]to obtain a quaternary ammonium salt polymer represented by the generalformula (6), and copolymerizing the monomer with acrylonitrile[High-Polymer Fiber Material Research Institute, Research Report, No.159 (1988) , pp. 17˜22]. However, these polymers still remain to beimproved in antibacterial activity. ##STR5##

Further U.S. Pat. No. 4,009,201 discloses that a polymer is produced bypreparing a cationic monomer represented, for example, by the formula(7) and polymerizing the monomer, but merely states that the polymer isfor use as an absorber or is useful for giving improved antistatic orpigment accepting effects, and says nothing whatever about antibacterialapplications. Additionally, the monomer, wherein a polymerizable vinylgroup is linked to a functional group having a cationic group by armester group, is susceptible to hydrolysis, so that the polymer derivedfrom the cationic monomer has the problem that the side chain containingthe cationic group (diammonium group) dissolves out as released from thepolymer main chain to impair the function of the polymer. ##STR6##

Among these researches, we have already found the compounds disclosed inU.S. Pat. No. 4,826,924 and the compounds disclosed in JP-A-342504/1992as compounds which are especially excellent in antibacterial activity.These compounds are prepared conventionally by reacting a tertiary aminewith a polymer having a reactive chlorine group on the side chain andsubstituting the tertiary amine for the reactive chlorine group, whereasit is difficult to completely effect the substitution of the tertiaryamine or like compound having a great molecular weight. The reactiontherefore requires a prolonged period of time or involves the likelihoodthat the chlorine group will remain unreacted in the molecule to impairthe safety and stability of the polymer.

Accordingly, we have conducted continued research to ensure highersafety and, at the same time, to simplify the reaction process. In thecourse of the research, an attempt was made, for example, to substitutea third component, such as an alkyl ammonium salt, which is lower inmolecular weight and easy to substitute, for the unreacted chlorinegroup, and a corresponding result was achieved. To obtain the desiredcomposition with greater ease, the result was nevertheless stillunsatisfactory from the viewpoint of simplifying the reaction processand the stability of the polymer in respect of quaternization andpolydispersity.

Further in the case of compounds (2) wherein A is phenylene which mayhave a substituent, a problem arises when the compound is present in amedium, such as water or alcohol, which has nucleophilic reactivity.Since the benzyl group is highly reactive, the compound is likely todecompose in the solvent, permitting the amine-containing side chain tobecome released or becoming degraded or insoluble while being stored fora long period. Furthermore, since the compound is not always fullyamenable to adsorption to a wide variety of carriers, articles forexample of acrylic, urethane or like sheet or fibers having the compoundapplied thereto fail to semipermanently retain an antibacterial effect.To solve this problem, we have devoted efforts to the preparation andscreening of peripheral substances and found substances having highsafety for use in such a field.

An object of the present invention is to provide a polymerizable monomerfor readily giving an antibacterial polymer which is excellent inbactericidal activity, high in safety and stability and capable ofretaining its effect for a prolonged period of time even in a reactiveenvironment, and to provide the polymer and a process for preparing thesame.

The present invention provides a polymerizable monomer represented bythe general formula (1) ##STR7## wherein R¹ is a hydrogen atom, methyl,chlorine or cyano, R² is alkylene having 1 to 4 carbon atoms, R³ isalkylene having 3 to 10 carbon atoms, R¹ is alkyl having 6 to 18 carbonatoms, R⁵ to R⁸ are the same or different and are each alkyl orsubstituted alkyl having 1 to 3 carbon atoms, A is methylene, phenylene,substituted phenylene, --CH₂ O--, --CH₂ CH₂ O--, --CO--, --CO--N(R⁹)--(wherein R⁹ is a hydrogen atom or methyl) or vinylene, m is 0 or 1, aridX and Y are the same or different, and are each a monovalent anion orform a bivalent anion when taken together.

The present invention further provides a polymer which has a structuralunit derived from noncrosslinkable or crosslinkable vinyl monomer orfrom a mixture of such monomers, and a structural unit represented bythe general formula (2) ##STR8## wherein R¹ is a hydrogen atom, methyl,chlorine or cyano, R² is alkylene having 1 to 4 carbon atoms, R³ isalkylene having 3 to 10 carbon atoms, R⁴ is alkyl having 6 to 18 carbonatoms, R⁵ to R⁸ are the same or different and are each alkyl orsubstituted alkyl having 1 to 3 carbon atoms, A' is methylene, --CH₂O--, --CH₂ CH₂ O--, --CO--, --CO--N(R⁹)-- (wherein R⁹ is a hydrogen atomor methyl) or vinylene, m is 0 or 1, and X and Y are the same ordifferent, and are each a monovalent anion or form a bivalent anion whentaken together.

The present invention further provides a process for preparing a polymercharacterized by polymerizing a noncrosslinkable or crosslinkable vinylmonomer or a mixture of such monomers with a monomer represented by thegeneral formula (1).

The present invention further provides a disinfectant compositioncomprising the polymer for destroying bacteria which are resistant toantibiotics.

The present invention further provides a method of impartingantibacterial properties to fibers by applying the polymer to thefibers.

In the compound represented by the general formula (1), especiallypreferable as the alkylene group represented by R³ is a group having 4to 6 carbon atoms from the viewpoint of antibacterial properties.Further preferable as the alkyl group represented by R⁴ is a grouphaving 10 to 14 carbon atoms from the viewpoint of antibacterialproperties because it is thought that the hydrophobicity of thefunctional group and the electron density of quaternary ammonium on thefunctional group have a close relation with antibacterial properties.

With reference to the general formula (1), examples of substituents onthe substituted phenylene represented by A are halogen atom such asfluorine, chlorine, bromine and iodine, lower alkyl such as methyl,ethyl, propyl and butyl, lower alkoxyl such as methoxy, ethoxy, propoxyand butoxy. Although the anions represented by X and Y are not limitedspecifically insofar as they are capable of neutralizing positivecharges, examples of useful anions are monovalent anion such as chlorineion, bromine ion, iodine ion, nitrate on, perchloration, acetate ion,methylsulfate ion, benzenesulfonate ion, chlorobenzenesulfonate ion andtoluene sulfonate ion, bivalent anion such as sulfate ion and methylphosphate ion.

Among the compounds of the general formula (1), the compound (1a)wherein the group represented by A is methylene, phenylene, substitutedphenylene, --CO--, --CO--N(R⁹)-- (wherein R⁹ is as defined above) orvinylene can be prepared, for example, by reacting a compoundrepresented by the general formula (8) with a compound represented bythe general formula (9). ##STR9## wherein R³ to R⁸ and X are as definedabove. ##STR10## wherein R¹, R², m and Y are as defined above, A¹ ismethylene, --CO--, --CO--N(R⁹)--, (wherein R⁹ is as defined above) orvinylene.

The reaction is conducted usually in a solvent, with heating ifrequired. The solvent is not limited specifically insofar as it does notinfluence the reaction. Examples of useful solvents are methanol,ethanol, propanol and like alcohols, dimethyl ether, tetrahydrofuran andlike ethers, benzene, toluene and like aromatic hydrocarbons,dichloromethane, carbon tetrachloride and like halogensted hydrocarbons,acetone, ethyl acetate, dimethyl sulfoxide and dimethylformamide. Sincethe desired product (2a) and the compound (9) are both polymerizable,the reaction may be conducted with a usual polymerization inhibitor,such as hydroquinone or catechol, added to the reaction system when sorequired. The mixing ratio of the compound (9) to the compound (8) isnot limited specifically but can be determined suitably from a widerange. The compound is used usually in an amount of about 0.7 to about0.2 moles, preferably about 0.9 to about 1.0 mole, per mole of thecompound (8).

The mono quaternary ammonium salt derivative of the general formula (8)is prepared, for example, by reacting an alkanediamine derivativesubstituted with lower alkyl and represented by the general formula (10)with a compound represented by the general formula (11) in a solvent orin the absence of solvent, with application of heat when required.##STR11## wherein R³ and R⁵ to R⁸ are as defined above.

    R.sup.4 X                                                  (11)

wherein R⁴ is as defined above.

The solvent is not limited specifically insofar as it produces noinfluence on the reaction. Examples of useful solvents are methanol,ethanol and like lower alcohols, acetonitrile and like nitriles, andtetrahydrofuran and like ethers. Although the mixing ratio of thecompound (10) to the compound (11) is not limited specifically, usuallyabout 1.0 to about 5 moles, preferably about 1.2 to about 4 moles, ofthe compound (10) is used per mole of the compound (11).

Examples of useful compounds (10) areN,N,N',N'-tetramethyl-1,3-propanediamine,N,N,N',N'-tetramethyl-1,4-butanediamine,N,N,N',N'-tetramethyl-1,5-pentanediamine,N,N,N',N'-tetramethyl-1,6-hexanediamine,N,N,N',N'-tetramethyloctanediamine, N,N,N',N'-tetramethyldecanediamine,N,N,N',N'-tetraethylethylenediamine,N,N,N',N'-tetraethyl-1,3-propanediamine,N,N,N',N'-tetraethyl-1,4-butanediamine,N,N,N',N'-tetraethyl-1,5-pentanediamine andN,N,N',N'-tetraethyl-1,6-hexanediamine. Examples of useful compounds(11) are those having about 6 to about 18 carbon atoms, such as alkylchloride, alkyl bromide, alkyl iodide, alkyl benzenesulfonate, alkylchlorobenzenesulfonate and alkyl toluenesulfonate.

Examples of useful compounds (9) are alkyl halides or methallyl halideswherein the halogen atom is chlorine, bromine or iodine, allylbenzenesulfonate, allyl chlorbenzenesulfonate, allyl toluenesulfonate,chloromethylstyrene, chloromethyl vinyl ketone, bromomethyl vinylketone, methallyl benzenesulfonate, methallyl chlorobenzenesulfonate,methallyl toluenesulfonate, α-methyl (chloromethyl) styrene, α-chloro(chloromethyl) styrene, α-cyano (chloromethyl) styrene,α-chloromethylacrylonitrile, N-2-chloroethylacrylamide,N-2-bromoethylacrylamide, N-methyl-N-2-bromoethylacrylamide,N-2-bromoethylmethacrylamide, N-methyl-N-2-bromoethylmethacrylamide,N-2-tosyloxyethylacrylamide andN-methyl-N-2-tosyloxyethylmethacrylamide.

The compound (1b) of the formula (1) wherein the group represented by Ais --CH₂ O-- or --CH₂ CH₂ O-- can be prepared, for example, by reactinga compound represented by the general formula (12) with a compoundrepresented by the general formula (13). ##STR12## wherein R² to R⁸, Xand Y are as defined above. ##STR13## wherein R¹ is as defined above, A²is methylene or ethylene, Z is a halogen atom, lower alkoxyl having 1 to4 carbon atoms, lower acyloxy having 2 to 5 carbon atoms,benzenesulfonyloxy, chlorobenzenesulfonyloxy, tosyloxy ormethanesulfonyloxy. Examples of lower acyloxy groups are acetyloxy,propionyloxy, butyryloxy and valeryloxy.

The reaction is carried out usually in a solvent in the presence of abase, with application of heat when required. The solvent is not limitedspecifically insofar as it produces no influence on the reaction.Examples of useful solvent are ether, tetrahydrofuran, dichloromethane,chloroform, dimethylformamide, dimethyl sulfoxide, etc. Since thedesired product (2b) and the compound (13) are both polymerizable, thereaction may be carried out with hydroquinone, catechol or like usualpolymerization inhibitor added to the reaction system when so required.The base is used usually in an approximately stoichiometric amountalthough the amount is not limited specifically. While the mixing ratioof the compound (12) to the compound (13) is not limited specifically,usually about 0.7 to about 1.2 moles, preferably about 0.9 to about 1.0mole, of the compound (12) is used per mole of the compound (13).

The base to be used is not limited specifically but can be a usual one.Examples of useful bases include inorganic bases such as sodiumhydroxide, potassium hydroxide and sodium carbonate, and organic basessuch as pyridine, piperidine, diisopropylamine, triethylamine anddiazabicyclooctane.

Examples of useful compounds (13) are allyl halides or methallyl halideswherein the halogen atom is chlorine, bromine or iodine,4-bromo-1-butene, 3-butenyl toluenesulfonate, esters of benzenesulfonicacid, toluenesulfonic acid or chlorobenzenesulfonic acid with allylalcohol or methallyl alcohol, and 2,3-dichloropropene.

The compound (12), which is a known substance, can be prepared, forexample, by reacting a compound (8) with a compound represented by thegeneral formula (14).

    HO--R.sup.2 Y                                              (14)

wherein R² and Y are as defined above.

The reaction is conducted usually in a solvent which will not exert anyinfluence on the reaction while heating the reaction system when sorequired. Although the mixing ratio of the compound (14) to the compound(8) is not limited specifically, usually about 1.0 to about 3 moles,preferably about 7.2 to about 2 moles, of the compound (14) is used permole of the compound (8). Examples of useful compounds (14) are2-halogeno-1-ethanol, 3-halogeno-1-propanol, 4-halogeno-1-butanol,3-halogeno-2-methyl-1-propanol (wherein halogen atom is chlorine,bromine, iodine atom, etc.), 2-hydroxyethyl benzenesulfonate,2-hydroxyethyl toluenesulfonate, 3-hydroxypropyl toluenesulfonate and4-hydroxybutyl toluenesulfonate.

The compound (12) can also be produced, for example, by the processcomprising protecting the hydroxyl group of the compound (14) with asuitable functional group W to obtain a compound represented by thegeneral formula (14a), reacting this compound with the compound (8) toprepare a compound represented by the general formula (12a) andhydrolyzing the resulting compound. The functional group represented byW is, for example, acetyl, tetrahydropyranyl, methoxymethyl,benzenesulfonyl, toluenesulfonyl or the like.

    WO--R.sup.2 Y                                              (14a)

wherein R² and Y is as defined above, and W is the functional group.##STR14## wherein R² to R⁸, X, Y and W are as defined above.

The reaction between the compound (8) and the compound (14a) is carriedout in a suitable solvent, with application of heat when so required.The solvent is not limited particularly insofar as it exerts noinfluence on the reaction. For example, the same solvent as is used forpreparing the compound (8) is usable. The amount of the compound (14a)to be used is not limited specifically but can be determined suitablyfrom a wide range. It is usually about 1.0 to about 3 moles, preferablyabout 1.2 to about 2 moles, per mole of the compound (8). Examples ofcompounds (14a) are 2-halogenoethyl acetate, 2-halogenoethyltetrahydropyranyl ether, 4-halogenobutyl toluenesulfonate (whereinhalogen atom is chlorine, bromine, iodine atom, etc.), ethylene glycolblsbenzenesulfonate and ethylene glycol bistoluenesulfonate.

The compound (12a) is hydrolyzed by a usual method. The compound (12a)can be readily converted to the compound (12), for example, by treatingthe compound in dilute hydrochloric acid, with heating when necessary.

The compounds (1) and intermediates thereof obtained by the foregoingreactions can be isolated and purified by usual methods such asfiltration, extraction, concentration and recrystallization.

The copolymer of the present invention can be produced by subjecting anoncrosslinkable or crosslinkable vinyl monomer or a mixture of suchmonomers, and the compound (1) to a usual polymerization process such assolution polymerization, solid-phase polymerization, bulkpolymerization, emulsion polymerization or suspension polymerization.Among these processes, it is desirable to use the solutionpolymerization process. The type of solvent to be used for the processis not limited particularly insofar as the solvent produces no adverseeffect on the reaction. Examples of solvents usable are protonic solventsuch as water, methanol, ethanol and propanol, ether solvent such asether, tetrahydrofuran and dioxane, halogenated hydrocarbon such aschloroform and carbon tetrachloride, aromatic hydrocarbon such asbenzene and toluene, nitrile solvent such as acetonitrile andpropionitrile, aprotic polar solvent such as dimethylformamide, dimethylacetamide, hexamethylphosphoric triamide and dimethyl sulfoxide.

Examples of useful noncrosslinkable vinyl monomers are styrene,p-methylstyrene, p-bromostyrene, p-chlorostyrene, α-chlorostyrene,α-bromostyrene or like polymerizable aromatic compound; acrylic acid,methyl acrylate, ethyl acrylate, lauryl acrylate, methylα-chloroacrylate, 2-hydroxyethyl acrylate, methyl methacrylate, ethylmethacrylate, propyl methacrylate, butyl methacrylate, laurylmethacrylate or like polymerizable carboxylic acid ester and saltthereof; vinyl acetate, vinyl trifluoroacetate, vinyl butyrate, vinylbenzoate or like vinyl ester monomer; vinyl chloride, vinyl fluoride,vinylidene chloride, vinylidene fluoride or like halogenated vinylmonomer; isobutyl vinyl ether, n-butyl vinyl ether or like vinyl ethermonomer; acrylamide, N-methyl acrylamide, N-ethyl acrylamide, N-methylmethacrylamide, N-ethyl methacrylamide or like polymerizable amide;acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylidenecyanide or like polymerizable nitrile; ehtylene, propylene, isobutylene,pentene, hexene, cyclohexene, norbornene, allene, butadiene, isoprene,chloroprene or like olefinic monomer; alkyl vinyl sulfide or like vinylsulfide monomer; N-vinylcarbazole, 4-vinylpyridine, N-vinylpyrrolidoneor like nitrogen-containing heterocyclic monomer; methyl vinyl ketone,phenyl vinyl ketone or like vinyl ketone monomer; maleic acid, maleicanhydride, acrolein, acrylic acid chloride, vinyl isocyanate, vinylsilane, allyl silane, polymerizable monomer represented by the formula(1).

Examples of useful crosslinkable vinyl monomers are divinylbenzene,divinylnaphthalene and the like. These monomers are usable singly, or atleast two of them can be used in mixture.

The charge molar ratio of the compound of the formula (1) of theinvention to the monomer to be copolymerized therewith is usually about0.001˜99.0: 99.999˜1.0, preferably about 1˜50: 99˜50.

The polymerization reaction can be conducted efficiently usually in thepresence of a polymerization initiator. Examples of usefulpolymerization initiators are azo initiator such as2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile,2,2'-azobis-2,4-dimethylvaleronitrile,1,1'-azobis-1-cyclohexanecarbonitrile anddimethyl-2,2'-azobisisobutyrate, peroxide such as hydrogen peroxide,benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, ammoniumpersulfate and potassium persulfate, redox initiater such as acombination of hydrogen peroxide or ammonium persulfate and sodiumsulfite or ferrous ion, organic metal compound such as phenylmagnesiumbromide and butyl lithium. The amount of the initiator to be used, whichdiffers with the kind thereof, mode of polymerization and desiredmolecular weight of the copolymer, is usually 1×10⁻⁵ ˜0.5 mole/l,preferably 1×10⁻⁴ ˜5×10⁻² mole/l.

In the case where the solution polymerization process is employed, thesolvent to be used is not limited specifically insofar as it exerts noadverse influence on the reaction. Examples of useful solvents areprotonic solvent such as water, methanol, ethanol, propanol, methylcellosolve and ethyl cellosolve, ether solvent such as ether,tetrahydroluran, dioxane, dimethoxyethane and diglyme, halogenatedhydrocarbon such as dichloromethane, chloroform and carbontetrachloride, aromatic hydrocarbon such as benzene, toluene and xylene,nitrile solvent such as acetonitrile and propionitrile, aprotic polarsolvent such as dimethylformamide, dimethyl acetamide,hexamethylphosphoric triamide and dimethyl sulfoxide. At least two ofthese solvents are usable in mixture.

The reaction temperature and the reaction time, although varying withthe reactivity of the monomer and the type of solvent used, aredetermined preferably from the respective ranges usually of 0° to 100°C. and 3 to 120 hours.

The copolymer can be isolated and purified by a usual method of aftertreatment. For example, the reaction mixture is added to an excessiveamount of solvent in which the product is sparingly soluble to separateout the product, which is then separated off as by filtration. When theproduct needs to be further purified, reprecipitation or likeconventional method is resorted to.

It is desired that the copolymer of the present invention be 1,000 to2,000,000, preferably 5,000 to 300,000, in number average molecularweight Mn and 1.1 to 2.0 in Mw/Mn (Mw: weight average molecular weight).Since the polymerization degree is governed by factors such as theconcentration of charges for the polymeriazation reaction, kind andconcentration of the initiator, reaction temperature and reaction time,a copolymer having the desired molecular weight and polydispersity canbe obtained by determining these factors in accordance with thesituation concerned.

The copolymer obtained is subjected to ion exchange by a known procedureto make the counter anion a monovalent anion such as chlorine ion,bromine ion, iodine ion, nitrate ion, perchlorate ion, acetate ion ormethylsulfate ion, or bivalent ion such as sulfate ion or methylphosphate ion.

For use as the active component, the polymers of the present inventionare usable singly, or at least two of them can be used in mixture.

The polymers of the invention can be in the form of a powder, granules,fibers, film or the like depending on the process for preparing thepolymer.

In the case where the polymers of the invention are used, for example,as the active component of antibacterial compositions, thesecompositions are usable for a wide variety of applications, for example,for tap water, cooling water, slime control, pools, fishing nets, shipbottoms, underwater structures, food packaging materials, buildingmaterials, agricultural materials, medical products, materials orutensils for use in the oral cavity (toothbrushes, toothpastes, etc.),spectacle frames, cosmetics, clothes and household utensils.

The present antibacterial polymers are usable by known methods. Forexample, for the antibacterial surface treatment of articles, thearticle can be treated by being dipped in or sprayed with a solutionprepared by dissolving one or at least two of the polymers in a suitablesolvent. At this time, the polymer is usable as admixed with knownpolymers.

The materials for which the antibacterial polymers are usable are, forexample, synthetic high polymers of any form such as polypropylene,polyethylene, polystyrene, polyester, polyamide, polyacrylate,polyurethane and polyvinyl chloride, natural high polymers such ascotton, wool, feathers, hemp, silk, paper and rubber, and further wood,glass, metal and ceramics.

These materials may be in the form of molded or shaped materials, orunprocessed materials. The material to be subjected to the antibacterialtreatment can be in the form of yarns, fibers, film, sheet, grains,powder or the like.

The polymers of the present invention impart high antibacterial activityto these materials with high safety over a prolonged period of time.

When the antibacterial polymers are to be used, it is generallypreferable to use the polymer as dissolved in methyl alcohol, ethylalcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutylalcohol, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulioxide or the like, or in a solvent mixture of such a solvent andacetone, tetrahydrofuran, benzene, toluene, xylene or the like. Theconcentration of the solution is 0.01 to 2.0 wt. %, preferably 0.1 to1.0 wt. %. The substance to be given antibacterial properties is dippedin or sprayed with the solution, whereby the solution is applied to thesurface, followed by drying to remove the solvent. It is desirable todry the wet substance in a drying chamber at a temperature of 0° to 80°C., preferably 20° to 60° C. for 10 to 48 hours.

The antibacterial polymers are also excellent in underwater antisoilingproperties. When to be used underwater for preventing soiling, theantibacterial polymer is usable as admixed with a known coatingcomposition. Known substances containing an antisoiling component can beadded to the mixture.

For underwater antisoiling applications, the antibacterial polymers areusable, for example, for fishing nets, ship bottoms, cooling waterpiping, buoys, dam gates, water tanks of culture facilities andunderwater structures, and are very effective for preventing adhesion ofsea weed, green layer, sea lettuce, barnacles, etc.

When the antibacterial polymers are to be used for underwaterantisoiling applications, it is generally desirable to dissolve thepolymer in a solvent such as methyl alcohol, ethyl alcohol, n-propylalcohol, isopropyl alcohol, n-butyl alcohol, N,N-dimethylformamide ordimethyl sulfoxide, or in a solvent mixture of such a solvent andbenzene, toluene, xylene or the like. The method of use can be a knownmethod.

The known substance containing an antisoiling component and usable asadmixed with the antibacterial polymer is not limited particularly.Examples of such substances are copper compounds, dithiocarbamatecompounds, phenarsazine compounds, quaternary ammonium salt compounds,etc. Also usable as admixed with the antibacterial polymer arecrosslinking agents, fillers, monomers, polymers and the like which haveantisoiling activity.

Next, the coating composition usable as mixed with the antibacterialpolymer may be any of those already known, which include, for example,acrylic acid resin, phthalic acid resin, aminoalkyd resin and syntheticresin emulsion compositions, lacquers, etc.

BEST MODE OF CARRYING OUT THE INVENTION

The invention will be described in detail with reference to thefollowing examples.

EXAMPLE 1

A 23.1 g quantity (0.16 mole) of N,N,N',N'-tetramethyl-1,4-diaminobutane(hereinafter referred to as "TMB") was dissolved in 50 ml ofacetonitrile, and 10.0 g (0.04 mole) of lauryl bromine was addeddropwise to the solution at room temperature with stirring, followed byheating at 70° C. for 3 hours. The reaction mixture was then cooled toroom temperature, giving a white precipitate, which gave 0.12 g ofN,N,N',N'-tetramethyl-1,4-diaminobutane-N,N'-dilauryl dibromide as aby-product (yield of by-product 1.0%) on filtration. The flitrate wasconcentrated at a reduced pressure to remove a major portion of the TMBand give a white pasty residue. The residue was washed with 40 ml ofhexane, and the hexane layer was separated off by decantation, giving awhite waxy substance free from any unreacted TMB. When thoroughly driedat a reduced pressure using a vacuum pump, the product gave 14.5 g ofN,N,N',N'-tetramethyl-1,4-N-lauryl bromide (hereinafter abbreviated as"TML-C₄ ", yield 92%). ¹ H-NMR (CDCl₃) δppm: 0.83 (t, 3H, CH₃),1.19˜1.29 (m, 20H, CH₂), 1.60˜2.00 (m, 6H, CH₂), 2.68 (s, 6H, CH₃ --N),3.05 (s, 6H, CH₃ --N), 3.15˜3.28 (m, 2H, CH₂ N), 3.37˜3.45 (m, 2H, CH₂N)

EXAMPLES 2 TO 5

The same reaction and aftertreatment as in Example 1 were repeatedexcept that TMB was replaced by 20.8 g (0.16 mole) ofN,N,N',N'-tetramethyl-1,3-diaminopropane (hereinafter abbreviated as"TMP"), 27.5 g (0.16 mole) of N,N,N',N'-tetramethyl- 1,6-diaminohexane(hereinafter abbreviated as "TMH"), 36.5 g (0.16 mole) ofN,N,N',N'-tetramethyl-1,10-diaminodecane (hereinafter abbreviated as"TMD") or 36.5 g (0.16 mole) of N,N,N',N'-tetraethyl -1,6-diaminohexane(hereinafter abbreviated as "TEH"), whereby the desired mono-quaternaryammonium salt derivatives were obtained. The reaction yielded a smallamount of bis-quaternary ammonium salt derivative as a by-product. Table1 shows the result, in which Et stands for ethyl.

EXAMPLES 6 AND 7

The desired mono-quaternary ammonium salt derivatives were obtained byrepeating the same reaction and aftertreatment as in Example 1 with theexception of using 27.5 g (0.16 mole) of TMH in place of TMB and 8.8 g(0.04 mole) of decyl bromide or 13.3 g (0.04 mole) of octadecyl bromideinstead of lauryl bromide. The reaction yielded a small ofbis-quaternary ammonium salt derivative as a by-product. Table 1 alsoshows the result.

                                      TABLE 1                                     __________________________________________________________________________                                        Yield                                     Ex.                                                                              Compound (10)                                                                          Compound (11)                                                                         Compound (8)    (%)                                       __________________________________________________________________________        ##STR15##                                                                             C.sub.12 H.sub.25 Br                                                                   ##STR16##      94                                        3                                                                                 ##STR17##                                                                             C.sub.12 H.sub.25 Br                                                                   ##STR18##      90                                        4                                                                                 ##STR19##                                                                             C.sub.12 H.sub.25 Br                                                                   ##STR20##      84                                        5                                                                                 ##STR21##                                                                             C.sub.12 H.sub.25 Br                                                                   ##STR22##      91                                        6                                                                                 ##STR23##                                                                             C.sub.10 H.sub.21 Br                                                                   ##STR24##      92                                        7                                                                                 ##STR25##                                                                             C.sub.18 H.sub.37 Br                                                                   ##STR26##      83                                        __________________________________________________________________________

EXAMPLE 8

A 11.1 g quantity (26.4 mmoles) of TML-C₆ obtained in Example 3 wasdissolved in 200 ml of acetone, and 3.7 g (24 mmoles) of4-chloromethylstyrene was added dropwise to the solution at roomtemperature with stirring. When the mixture was then heated at 50° C.for 17 hours, white crystals separated out. The reaction mixture wascooled to room temperature, and the resulting white crystals wereisolated by filtration, washed with cold acetone and thereafter dried,affording 12.0 g of N,N,N',N'-tetramethyl-N-lauryl-N'-(4-vinyl)benzylhexamethylene diammonium bromide chloride (hereinafter abbreviatedas "TMLS-C₆ ", yield 87%). ¹ H-NMR (CDCl₃)δppm: 0.86 (t, 3H, CH₃) ,1.92˜1.37 (m, 18H, CH₂), 1.53˜1.73 (m, 6H, CH₂) , 1.98˜2.21 (m, 4H,CH₂), 3.26 (s, 6H, CH₃ N), 3.37 (s, 6H, CH₃ N) , 3.40˜3.50 (m, 2H, CH₂N), 3.68˜3.87 (m, 4H, CH₂ N) , 4.95 (s, 2H, CH₂ Ar), 5.38 (d, 1H,vinyl), 5.81 (d, 1H, vinyl), 6.7 (dd, 1H, vinyl) , 7.46 (d, 2H, ArH) ,7.62 (d, 2H, ArH)

EXAMPLES 9 TO 12

The desired his-quaternary ammonium salt derivatives were obtained byrepeating the same reaction and aftertreatment as in Example 8 with theexception of using 2.90 g (24 mmoles) of allyl bromide, 3.24 g (24mmoles) of 4-bromo-1-butene, 3.58 g (24 mmoles) of bromomethyl vinylketone or 6.79 g (24 mmoles) of N-2-tosyloxyethylacrylamide in place of4-chloromethylstyrene and using acetone or ethyl acetate as a solvent.Table 2 shows the result.

                                      TABLE 2                                     __________________________________________________________________________       Compound (8)                                  Yield                        Ex.                                                                              (solvent)                                                                             Compound (9) Compound (1)             (%)                          __________________________________________________________________________     9                                                                                ##STR27##                                                                             ##STR28##                                                                                  ##STR29##               94                           10                                                                                ##STR30##                                                                             ##STR31##                                                                                  ##STR32##               88                           11                                                                                ##STR33##                                                                             ##STR34##                                                                                  ##STR35##               86                           12                                                                                ##STR36##                                                                             ##STR37##                                                                                  ##STR38##               80                           __________________________________________________________________________

EXAMPLES 13 TO 18

The desired bis-quaternary ammonium salt derivatives were obtained byrepeating substantially the same reaction and aftertreatment as inExample 8 with the exception of using 9.09 g (24 mmoles) of TML-C₃, 9.43g (24 mmoles) of TML-C₄, 12.4 g (26 mmoles) of TML-C₁₀, 10.2 g (26mmoles) of TMD-C₆, 13.1 g (26 mmoles) of TMO-C₆ or 12.4 g (26 mmoles) ofTEL-C₆. in place of TML-C₆. Table 3 shows the result.

                                      TABLE 3                                     __________________________________________________________________________       Compound (8)                                     Yield                     Ex.                                                                              (solvent)                                                                             Compound (9)  Compound (1)               (%)                       __________________________________________________________________________    13                                                                                ##STR39##                                                                             ##STR40##                                                                                   ##STR41##                 95                        14                                                                                ##STR42##                                                                             ##STR43##                                                                                   ##STR44##                 95                        15                                                                                ##STR45##                                                                             ##STR46##                                                                                   ##STR47##                 90                        16                                                                                ##STR48##                                                                             ##STR49##                                                                                   ##STR50##                 82                        17                                                                                ##STR51##                                                                             ##STR52##                                                                                   ##STR53##                 87                        18                                                                                ##STR54##                                                                             ##STR55##                                                                                   ##STR56##                 89                        __________________________________________________________________________

EXAMPLE 19

A 8.42 g quantity (20 mmoles) of TML-C₆ obtained in Example 3 wasdissolved in 200 ml of methanol, and 2.78 g (20 mmoles) of3-bromo-1-propanol was added to the solution of room temperature. Themixture was then reacted at 50° C. with heating for 12 hours andthereafter concentrated at a reduced pressure to obtain 11.1 g of whitesolid reaction. The residue was placed into 100 ml of ethyl acetate,followed by washing and then by filtration to remove the resultingsolution layer. When dried, the cake gave 9.96 g ofN,N,N',N'-tetramethyl-N-(3-hydroxy) propyl-N'-lauryl-hexamethylenediammonium dibromide (TMLP-C₆) in the form of white crystals (yield89%). ¹ H-NMR (CDCl₃) δppm: 0.87 (t, 3H, CH₃), 1.20˜1.57 (m, 26H, CH₂),1.63˜1.80 (m, 4H, CH₂), 3.25 (t, 2H, CH₂ O), 3.39 (s, 6H, CH₃ N), 3.50(s, 6H, CH₃ N), 3.45˜3.59 (m, 8H, CH₂ N)

EXAMPLE 20

Substantially the same reaction and aftertreatment as in Example 19 wererepeated except that 3-bromo-1-propanol was replaced by 4.88 g (20mmoles) of 4-tosyloxy-1-butanol, whereby 10.2 g ofN,N,N',N'-tetramethyl-N-(4-hydroxy)butyl-N'-laurylhexamethylenediammonium bromide toluenesulfonate (TMLB-C₆) was obtained in the formof white crystals (yield 91%). ¹ H-NMR (CDCl₃) δppm: 0.87 (t, 3H, CH₃) ,1.20˜1.56 (m, 30H, CH₂), 1.63˜1.82 (m, 4H, CH₂), 2.25 (s , 3H, CH₃ Ar),3.39 (s, 6H, CH₃ N), 3.49 (s, 6H, CH₃ N), 3.35˜3.63 (m, 8H, CH₂ N), 7.55(d, 2H, ArH) , 7.86 (d, 2H, ArH)

EXAMPLE 21

A 16.8 g quantity (40 mmoles) of TML-C₆ obtained in Example 3 wasdissolved in 200 ml of acetone, and 6.67 g (40 mmoles) of 2-bromoethylacetate was added to the solution at room temperature. The mixture wasreacted at 50° C. for 12 hours to obtain white crystals, which was thenisolated by filtration, affording 23.1 g ofN,N,N',N'-tetramethyl-N-(2-acetoxy)ethyl-N'-laurylhexamethylenediammonium dibromide. The product was dissolved in 120 ml of 2% dilutehydrobromic acid, followed by stirring at 60° C. for 15 hours. Theresulting reaction mixture was concentrated at a reduced pressure toobtain a light yellow waxy residue, which was then placed into ethylacetate, followed by washing and then by filtration for the removal of asolution layer. The cake was dried, affording 17.9 g ofN,N,N',N'-tetramethyl-N-(2-hydroxy)ethyl-N'-laurylhexamethylenediammonium dibromide (TMLE-C₆) in the form of substantially whitecrystals (yield 82%). ¹ H-NMR (CDCl₃) δppm: 0.86 (t, 3H, C₃), 1.22˜1.56(m, 24H, CH₂), 1.63˜1.79 (m, 4H, CH₂), 3.26 (t, 2H, CH₂ O ), 3.40 (s,6H, CH₃ N), 3.51 (s, 6H, CH₃ N), 3.46˜3.60 (m, 8H, CH₂ N)

EXAMPLE 22

A 5.46 g quantity (10 mmoles) of TMLE-C₆ obtained in Example 21 and 1.45g (12 mmoles) of allyl bromide were dissolved in 50 ml ofdichloromethane, and 1.01 g (10 mmoles) of triethylamine was addeddropwise to-the solution at room temperature with stirring. The mixturewas stirred at 40° C. for 15 hours and then cooled to room temperatureto form a white precipitate, which was filtered off. Concentration ofthe filtrate afforded a light yellow waxy residue. The residue wasthoroughly washed with acetone and thereafter dried, giving 4.2 g ofN,N,N',N'-tetramethyl-N-(2-allyloxy) ethyl-N'-laurylhexamethylenediammonium dibromide (TML2A-C₆) in the form of substantially whitecrystals (yield 72%). ¹ H-NMR (CDCl₃) δppm: 0.86 (t, 3H, CH₃), 1.22˜1.57(m, 24H, CH₂ ), 1.63˜1.80 (m, 4H, CH₂), 3.12 (d, 2H, CH₂ O), 3.26 (t,2H, CH₂ O), 3.40 (s, 6H, CH₃ N), 3.52 (s, 6H, CH₃ N), 3.45˜3.60 (m, 8H,CH₂ N), 5.39 (d, 1H, vinyl), 5.68 (m, 1H, vinyl) , 5.92 (d, 1H, vinyl)

EXAMPLE 23

A 3.44 g quantity (6 mmoles) of TMLS-C₆ and 5.62 g (54 mmoles) ofstyrene were dissolved in 10 ml of methanol, and a solution of 50 mg(0.3 mmole) of AIBN in 2 ml of methanol was added to the solution. Whenthe mixture was stirred in a nitrogen atmosphere at 65° C. for 22 hours,the mixture became a consistent solution. The reaction mixture wasplaced into water to terminate the polymerization reaction, and a whitepolymer formed was isolated by filtration and dried at a reducedpressure. The white polymer obtained was dissolved again in methanol,and the solution was placed into water. This procedure was repeatedtwice for purification and drying, whereby 6.3 g of white powderypolymer was obtained. The white powdery product was found to be acopolymer of TMLS-C₆ and styrene by TLC, IR and ¹ H-NMR analyses. Whenanalyzed by GPC (based on polystyrene) using dimethylformamide as asolvent, the copolymer was 158,000 in Mn and 1.4 in polydispersityMw/Mn. Quantitative determination of the quaternary ammonium content bycolloidal titration with use of polyvinyl sulfate potassium indicatedthat the TMLS-C₆ /styrene ratio of the copolymer was 73:87.

EXAMPLE 24

A white powdery polymer (5.9 g) was obtained by repeating the samereaction and aftertreatment as in Example 23 except that TMLS-C₆ wasreplaced by 3.79 g (6 mmoles) of TMLV-C₃. When analyzed by TLC, IR and ¹H-NMR, the white polymer was found to be a copolymer of TMLV-C₃ andstyrene.

Similarly, when analyzed by GPC, the copolymer was found to be 86,000 inMn and 7.8 in polydispersity Mw/Mn. Quantitative determination of thequaternary ammonium content by colloidal titration indicated that theTMLV-C₃ /styrene ratio of the copolymer was 9:91.

EXAMPLES 25 AND 26

White powdery polymers (6.3 g and 6.4 g) were prepared by repeating thesame reaction and aftertreatment as in Example 23 except that TMLS-C₆was replaced by 3.26 g (6 mmoles) of TMLV-C₄ or 3.78 g (6 mmoles) ofTMLV-C₁₀. When analyzed by TLC, IR and ¹ H-NMR, these polymers werefound to be copolymers of TMLV-C₄ or TMLV-C₁₀, and styrene.

GPC and colloidal titration conducted in the same manner as in Example23 revealed that the copolymer comprising TMLV-C₄ was 172,000 in Mn, 2.0in polydispersity Mw/Mn and 16:84 in the TMLV-C₄ /styrene ratio, andthat the copolymer comprising TMLV-C₁₀ was 62,000 in Mn, 2.2 inpolydispersity Mw/Mn and 7:93 in TMLV-C₁₀ /styrene ratio.

EXAMPLES 27 AND 28

White powdery polymers (6.6 g and 6.4 g) were prepared by repeating thesame reaction and aftertreatment as in Example 23 except that TMLS-C₆was replaced by 3.27 g (6 mmoles) of TMDV-C₆ or 3.95 g (6 mmoles) ofTMOV-C₆. When analyzed by TLC, IR and ¹ H-NMR, these polymers werecopolymers comprising TMDV-C₆ or TMOV-C₆.

GPC and colloidal titration conducted in the same manner as in Example23 revealed that the copolymer comprising TMDV-C₆ was 124,000 in Mn, 2.0in polydispersity Mw/Mn and 18:82 in the TMDV-C₆ /styrene ratio, aridthat the copolymer comprising TMOV-C₆ was 81,000 in Mn, 1.9 inpolydispersity Mw/Mn and 9:91 in the TMOV-C₆ /styrene ratio.

EXAMPLE 29

TMLS-C₆ (6.88 g, 12 mmoles) and 11.2 g (108 mmoles) of styrene weredissolved in 12 ml of methanol, and a solution of 32 mg (0.19 mmole) ofAIBN in 1 ml of methanol was added to the solution. The mixture became aconsistent solution when stirred in a nitrogen atmosphere at 65° C. for39 hours. The solution was aftertreated in substantially the same manneras in Example 23 to obtain 13.7 g of a white powdery polymer. The whitepolymer was found to be a copolymer of TMLS-C₆ and styrene by TLC, IRand ¹ H-NMR analyses.

When similarly analyzed by GPC, the copolymer was found to be 480,000 inMn and 1.9 in polydispersity Mw/Mn. Quantitative determination of thequaternary ammonium content by colloidal titration revealed that theTMLS-C₆ /styrene ratio was 10:90.

EXAMPLE 30

TMLS-C₆ (6.88 g, 12 mmoles) and 1.25 g (12 mmoles) of styrene weredissolved in 4 ml of methanol, and a solution of 20 mg (0.12 mmole) ofAIBN in 1 ml of methanol was added to the solution. Substantially thesame reaction and aftertreatment as in Example 23 were conducted toobtain 6.5 g of a white polymer. The white polymer was found to be acopolymer of TMLS-C₆ and styrene by TLC, IR and ¹ H-NMR analyses.

When analyzed by GPC, the copolymer was found to be 200,000 in Mn and1.6 in polydispersity Mw/Mn. Quantitative determination of thequaternary ammonium content by colloidal titration indicated that theTMLS-C₆ /styrene ratio was 64:36.

EXAMPLE 31

A white polymer (6.1 g) was obtained by conducting substantially thesame reaction and aftertreatment as in Example 23 except that styrenewas replaced by 5.40 g (54 mmoles) of methyl methacrylate. TLC, IR and ¹H-NMR analyses indicated that the polymer was a copolymer of TMLS-C₆ andmethyl methacrylate in the ratio of about 16:84.

When analyzed by GPC in the same manner as in Example 23, the copolymerwas 104,000 in Mn and 1.4 in polydispersity Mw/Mn.

EXAMPLE 32

The same reaction as in Example 23 was effected with the exception ofusing 3.89 g (54 mmoles) of acrylic acid instead of styrene. Thereaction mixture was placed into ether to terminate the polymerizationreaction to obtain a white precipitate, which was isolated by filtrationand dried to obtain 5.8 g of a white powdery polymer. TLC, IR and ¹H-NMR analyses revealed that the polymer was a copolymer of TMLS-C₆ andacrylic acid in the ratio of about 7:93.

When analyzed by GPC in the same manner as in Example 23, the copolymerwas 86,000 in Mn and 1.9 in polydispersity Mw/Mn.

EXAMPLE 33

TMLS-C₆ (3.44 g, 6 mmoles) and 8.52 g (60 mmoles) 50% aqueous solutionof acrylamide were dissolved in 10 ml of water, and a solution of 50 mg2,2'-azobis(2-amidopropane) dihydrochloride in 2 ml of water was addedto the solution to prepare a uniform solution. The solution was reactedin a nitrogen atmosphere at 50° C. for 2 hours to give a gel of reactionmixture. The gel was placed into an excess of dioxane to terminate thepolymerization reaction and form a white polymer, which was thenisolated by filtration and dried at a reduced pressure, giving 7.0 g ofwhite polymer. TLC, IR and ¹ H-NMR analyses indicated that the polymerwas a copolymer of TMLS-C₆ and acrylamide.

GPC analysis and colloidal titration conducted in the same manner as inExample 23 revealed that the copolymer was 328,000 in Mn, 1.9 inpolydispersity Mw/Mn and 8:92 in TMLS-C₆ /acrylamide ratio.

EXAMPLE 34

TMLS-C₆ (2.87 g, 5 mmoles) and 4.30 g (50 mmoles) of vinyl acetate weredissolved in 7 ml of dry DMF, and a solution of 41 mg (0.25 mmole) ofAIBN in 1 ml of DMF was added to the solution. The mixture became aconsistent solution when stirred in a nitrogen atmosphere at 60° C. for20 hours. The reaction mixture was placed into ether to terminate thepolymerization reaction to form a white polymer, which was then isolatedby filtration and dried at a reduced pressure, giving 4.6 g of whitepowder. The powder was found to be a copolymer of TMLS-C₆ and vinylacetate by TLC, IR and ¹ H-NMR analyses. When analyzed by GPC in thesame manner as in Example 23, the copolymer was found to be 73,000 in Mnand 1.6 in polydispersity Mw/Mn. Quantitative determination of thequaternary ammonium content by colloidal titration indicated that thecopolymer was 19:81 in TMLS-C₆ /vinyl acetate ratio.

EXAMPLE 35

A white powdery polymer (3.2 g) was obtained by conducting the samereaction and aftertreatment as in Example 34 except that vinyl acetatewas replaced by 2.65 g (50 mmoles) of acrylonitrile. TLC, IR and ¹ H-NMRanalyses revealed that the polymer was a copolymer of TMLS-C₆ andacrylonitrile. The copolymer was found to be 51,000 in Mn and 2.2 inpolydispersity Mw/Mn. Quantitative determination oi the quaternaryammonium content by colloidal titration indicated that the copolymer was17:83 in TMLS-C₆ /acrylonitrile ratio.

EXAMPLE 36

TMLS-C₆ (2.87 g, 5 mmoles), 5.21 g (50 mmoles) of styrene and 0.65 g (5mmoles) of divinylbenzene were dissolved in 20 ml of methanol, and asolution of 50mg (0.3 mmole) of AIBN in 2 ml of methanol was added tothe solution. The mixture gelled when stirred in a nitrogen atmosphereat 60° C. for 19 hours. The reaction mixture was placed into water toobtain a white rubberlike polymer, which was then isolated by filtrationand dried at a reduced pressure. The resulting white polymer was washedwith methanol under reflux, and the resulting methanol containing thepolymer as swollen was placed into cold methanol. The white polymerseparating out was isolated by filtration and dried at a reducedpressure, affording 7.0 g of white polymer. The polymer was sparinglysoluble in a majority of solvents. TLC, IR and ¹ H-NMR (hot DMSO-d₆)analyses revealed that the polymer was a crosslinked copolymercomprising TMLS-C₆, styrene and divinylbenzene. The quaternary ammoniumcontent was found to be 1.25 millieq/g.

EXAMPLE 37

A white polymer (4.9 g) was prepared by repeating the same reaction andaftertreatment as in Example 23 with the exception of using 3.25 g (6mmoles) of TMLA-C₆ in place of TMLS-C₆ and 40 mg of2,2'-bis(N-phenylamidinyl)-2,2'-azopropane dihydrochloride in place ofAIBN. TLC, IR and ¹ H-NMR analyses indicated that the white polymer wasa copolymer of TMLA-C₆ and styrene. The copolymer was found to be 42,000in Mn and 2.2 in polydispersity Mw/Mn by GPC analysis. Quantitativedetermination of the quaternary ammonium content by colloidal titrationrevealed that the copolymer was 0.5:99.5 in TMLA-C₆ /styrene ratio.

EXAMPLE 38

A white polymer (5.2 g) was prepared by repeating the same reaction andaftertreatment as in Example 23 with the exception of using 3.33 g (6mmoles) of TMLB-C₆ instead of TMLS-C₆ and 40 mg of2,2'-bis(N-phenylamidinyl)-2,2'-azopropane dihydrochloride in place ofAIBN. The polymer was found to be a copolymer of TMLB-C₆ and styrene byTLC, IR and ¹ H-NMR analyses. The copolymer was found to be 48,000 in Mnand 2.4 in polydispersity Mw/Mn by GPC analysis. Quantitativedetermination of the quaternary ammonium content by colloidal titrationindicated that the TMLB-C₆ /styrene ratio of the copolymer was 1:99.

EXAMPLE 39

A white polymer (4.4 g) was obtained by repeating the same reaction andaftertreatment as in Example 23 except to that TMLS-C₆ was replaced by3.42 g (6 mmoles) of TMLK-C₆. The polymer was found to be a copolymer ofTMLK-C₆ and styrene by TLC, IR and ¹ H-NMR analyses. Similarly, thecopolymer was found to be 101,000 in Mn, 1.8 in polydispersity Mw/Mn and5:95 in TMLK-C₆ /styrene ratio.

EXAMPLE 40

A white polymer (4.6 g) was obtained by repeating the same reaction andaftertreatment as in Example 23 except that TMLS-C₆ was replaced by 4.22g (6 mmoles) of TMLC-C₆. The polymer was found to be a copolymer ofTMLC-C₆ and styrene by TLC, IR and ¹ H-NMR analyses. The copolymer wasfound to be 90,000 in Mn, 1.7 in polydispersity Mw/Mn and 6:94 inTMLC-C₆ /styrene ratio similarly by GPC analysis and colloidaltitration.

EXAMPLE 41

A white polymer (7.0 g) was obtained by repeating the same reaction andaftertreatment as in Example 23 except that TMLS-C₆ was replaced by 3.78g (6 mmoles) of TELV-C₆. TLC, IR and ¹ H-NMR analyses revealed that thepolymer was a copolymer of TELV-C₆ and styrene. The copolymer was foundto be 40,000 in Mn, 1.9 in polydispersity Mw/Mn and 12:88 in TELV-C₆/styrene ratio.

COMPARATIVE EXAMPLE 1

To carry out a reaction for preparing a copolymer from styrene(abbreviated as "ST") and 4-chloromethylstyrene (abbreviated as "CS") bythe usual solution polymerization process, 77.0 g (0.74 mole) of styrenewas reacted with 9.2 g (0.06 mole) of 4-chloromethylstyrene in 40 mltetrahydrofuran in the presence of 0.66 g (4 mmoles) of AIBN at 60° C.for 20 hours. The mixture was placed into THF/methanol, followed byreprecipitation for purification, then by isolation through filtrationand thereafter by drying in a vacuum to obtain 73.3 g of a white powderypolymer (abbreviated as "PCS"). The polymer was found to be atwo-component copolymer, for example, by TLC, ¹ H-NMR and GPC analyses.

Total halogen quantitative analysis by the oxygen flask combustionmethod and elementary analysis revealed that the PCS was 91.7:8.3 inST/CS molar ratio.

GPC determination (calculated as polystyrene) with use oi THF as asolvent indicated that the PCS was 134,000 in number average molecularweight Mn and 1.57 in polydispersity Mw/Mn.

Next, 19.6 g of the PCS thus prepared was dissolved in 500 ml of THF,7.07 g (18 mmoles) of the TML-C₄ obtained in Example 1 was added to thesolution, and the mixture was reacted at 80° C. for 21 hours. Thereaction mixture was cooled to room temperature and then placed intowater. The resulting precipitate was filtered oil and dried, giving awhite polymer. The polymer was dissolved in water, followed byreprecipitation from water twice for purification and then by drying toobtain 23.4 g of a white powdery polymer. The polymer was found to bethe desired product comprising PCS having TML-C₄ introduced therein, forexample, by TLC and ¹ HNMR analyses.

The polymer was checked by the oxygen flask combustion method for totalhalogen quantitative determination, by the silver nitrate titrationmethod for ionic halogen quantitative determination, by elementaryanalysis for the determination of N % and by the colloidal titrationmethod for the quantitative determination of quaternaly ammonium contentto calculate the content of ST units, the content of remainingchloromethyl groups, i.e., of CS units and the amount of TML-C₄ unitssupported. The calculated values were 91.7 mole 96, 0.5 mole % and 7.8mole %, respectively.

Comparative Test Example 1

The polymers obtained in Example 25 and Comparative Example 1 were eachplaced into a glass container, then allowed to stand in a constanttemperature bath adjusted to 50° C. and shielded from light, andthereafter checked for changes with time. One week later, no change wasfound in the polymer of Example 25, whereas the polymer of ComparativeExample 1 was found slightly yellowed, with evolution of acid gas whichturned pH test paper red. Twenty days later, the polymer of Example 25was found unchanged in appearance and satisfactory in solubility inmethanol, while a major or portion of the polymer of Comparative Example1 was found degraded to a substance which was insoluble in methanol.

TEST EXAMPLE 1 Preparation of antibacterial fabric

For use as a test compound, the compound prepared in Example 23 wasdissolved in methanol to obtain 0.1, 0.2 and 0.5 wt. % methanolsolutions. Next cotton shirting, JIS standard fabric (hereinafterreferred to as the "fabric"), was dipped in the methanol solution forpadding. Next, the fabric was immediately checked for weight andthereafter cured at 105° C. for 30 minutes to completely fix the testcompound to the fabric. The fabric was used as an "antibacterial fabric"for the following test.

The weight (mg/g fabric) of test compound fixed to the antibacterialfabric is expressed by the following equation (1):

    C=(B-A) (W/100) (1/A) (1000)                               (I)

A: initial weight. (g/predetermined area) of the fabric

B: weight (g/predetermined area) of the fabric immediately before curing

C: weight (mg/g fabric) of test compound fixed to the antibacterialfabric

W: concentration (wt. %) of the methanol solution of test compound

From Equation (1), the following relationship was established betweenthe value W and the value C.

    ______________________________________                                        W (concn. of methanol soln.                                                                     C (wt. of test compound                                     of test compound) fixed to fabric)                                            (wt. %)           (mg/g fabric)                                               ______________________________________                                        0.1               1.0                                                         0.2               2.0                                                         0.5               5.0                                                         ______________________________________                                    

Antibacterial Test

The "antibacterial fabric" thus obtained was tested according to TheSociety for Antibacterial and Antifungal Agents, Japan, "Method ofTesting Textile Products Subjected to Antibacterial Treatment forInhibition of Growth of Bacteria" (hereinafter referred to as the"antibacterial textile test method"). The strains of test bacteria arethose prescribed for the method plus Pseudomonas aeruginosa ATCC 10145.Thus, five strains were used which were Staphylococcus aureus FDA 209P,Bacillus subtilis ATCC 6633, Klebsiella pneumoniae ATCC 4352,Escherichia coli IFO 3301 and Pseudomonas aeruginosa ATCC 10145. As tothe method of counting the number of live cells, reference was made to"Antibacterial and Antimold Handbook," edited by The Society forAntibacterial and Antifungal Agents, Japan, 1986, pp.678˜691.

Expression of Results

The test results were expressed following the procedure described below.The bactericidal index was given by Equation (II).

    Bactericidal index=log N(I)-log N(D)                       (II)

    Bactericidal index=log N(I)-log N(D)                       (II)

wherein N(I) is the initial number of cells, and N(D) is the number ofcells in the group to which the chemical agent (specimen) was added.

Next, such bactericidal indices were expressed according to thefollowing four criteria of:

    ______________________________________                                        Bactericidal index of less than 1                                                                         . . . 1                                           Bactericidal index of at least 1 to less than 2                                                           . . . 2                                           Bactericidal index of at least 2 to less than 3                                                           . . . 3                                           Bactericidal index of at least 3                                                                          . . . 4                                           ______________________________________                                    

Table 4 shows the results.

                                      TABLE 4                                     __________________________________________________________________________    Bactericidal Test: weight (mg/g fabric) of                                    Test Compound Fixed to "Antibacterial Fabric"                                     S. aureus                                                                           B. subtilis                                                                          K. pneumoniae                                                                         E. coli                                                                            P. aeruginosa                                   weight                                                                            FDA 209P                                                                            ATCC 6633A                                                                           ATCC 4352                                                                             IFO 3301                                                                           ATCC 10145                                      __________________________________________________________________________    1.0 mg                                                                            3     3      3       3    3                                               2.0 mg                                                                            3     3      3       3    3                                               5.0 mg                                                                            4     4      4       4    4                                               __________________________________________________________________________

EXAMPLES 42 AND 43

The desired allyl ether derivatives were prepared by repeatingsubstantially the same reaction and aftertreatment as in Example 22except that TMLE-C₆ was replaced by 5.61 g (10 mmoles) of TMLP-C₆obtained in Example 19 or by 6.70 g (10 mmoles) of TMLB-C₆ obtained inExample 20. Table 5 shows the results.

                                      TABLE 5                                     __________________________________________________________________________       Compound                                                                      (12)     Compound                                                                              Compound                  Yield                           Ex.                                                                              (solvent)                                                                              (13)    (1b)                      (%)                             __________________________________________________________________________    42                                                                                ##STR57##                                                                              ##STR58##                                                                             ##STR59##                74                              43                                                                                ##STR60##                                                                              ##STR61##                                                                             ##STR62##                70                              __________________________________________________________________________

EXAMPLES 44 TO 46

The same reaction and aftertreatment as in Example 37 were repeated withthe exception of using 9.05 g (15 mmoles) of TML2A-C₆ obtained inExample 22, 9.30 g (15 mmoles) of TML3A-C₆ obtained in Example 42 or10.8 g (15 mmoles) of TML4A-C₆ obtained in Example 43, in place ofTMLA-C₆, whereby 4.9 g, 5.0 g and 5.4 g of white powdery polymers wereobtained, respectively. TLC, IR and ¹ H-NMR analyses revealed that thesepolymers were copolymers of styrene, and TML2A-C₆ (Example 44) orTML3A-C₆ (Example 45) or TML4A-C₆ (Example 46). The polymer obtained inExample 44 was 78,000 in Mn and 3.6 in polydispersity Mw/Mn, the polymerobtained in Example 45 was 83,000 in Mn and 4.1 in polydispersity Mw/Mn,and the polymer obtained in Example 46 was 101,000 in Mn and 2.9 inpolydispersity Mw/Mn, as determined by GPC analysis. Quantitativedetermination of the quaternary ammonium content by colloidal titrationrevealed that the copolymers were composed of TML2A-C₆, TML3A-C₆ orTML4A-C₆, and styrene in the ratio of 4.0:96.0, 2.8:97.2 or 4.5:95.5,respectively.

EXAMPLES 47 TO 49 Preparation of antibacterial fabric

The compounds prepared in Examples 23, 40 and 45 were used in Examples47 to 49, respectively, as test compounds. Each of these compounds wasdissolved in methanol to obtain 0.1, 0.2 and 0.5 wt. % methanolsolutions. Next, cotton shirting, JIS standard fabric (hereinafterreferred to as the "fabric"), was dipped in the methanol solution forpadding. Next, the fabric was immediately checked for weight andthereafter cured at 105° C. for 30 minutes to completely fix the testcompound to the fabric. The fabric was used as an "antibacterial fabric"for the following test.

The weight (mg/g fabric) of test compound fixed to the antibacterialfabric is expressed by the foregoing equation (I):

    C=(B-A) (W/100) (1/A) (1000)                               (I)

A: initial weight (g/predetermined area) of the fabric

B: weight (g/predetermined area) of the fabric immediately before curing

C: weight (mg/g fabric) of test compound fixed to the antibacterialfabric

W: concentration (wt. %) of the methanol solution of test compound

From Equation (I), the following relationship was established betweenthe value W and the value C.

    ______________________________________                                              W (concn. of methanol soln.                                                                     C (wt. of test compound                                     of test compound) fixed to fabric)                                      Ex.   (wt. %)           (mg/g fabric)                                         ______________________________________                                        47    0.1               1.0                                                         0.2               2.0                                                         0.5               5.0                                                   48    0.1               1.0                                                         0.2               2.1                                                         0.5               5.3                                                   49    0.1               1.1                                                         0.2               2.2                                                         0.5               5.3                                                   ______________________________________                                    

TEST EXAMPLE 2 (ANTIBACTERIAL TEST)

The "antibacterial fabric" thus obtained was tested according to TheSociety for Antibacterial and Antifungal Agents, Japan, "Method ofTesting Textile Products Subjected to Antibacterial Treatment forInhibition of Growth of Bacteria" (hereinafter referred to as the"antibacterial textile test method"). The strains of test bacteria arethose prescribed for the method plus Pseudomonas aeruginosa ATCC 10145.Thus, five strains were used which were Staphylococcus aureus FDA 209P,Bacillus subtills ATCC 6633, Klebsiella pneumoniae ATCC 4352,Escherichia coli IFO 3301 and Pseudomonas aeruginosa ATCC 10145. As tothe method of counting the number of live cells, reference was made to"Antibacterial and Antimold Handbook," edited by The Society forAntibacterial and Antifungal Agents, Japan, 1986, pp.678˜691.

Expression of Results

The test results were expressed following the procedure described below.The bactericidal index was given by Equation (II).

    Bactericidal index=log N(I)-log N(D)                       (II)

wherein N(I) is the initial number of cells, and N(D) is the number ofcells in the group to which the chemical agent (specimen) was added.

Next, such bactericidal indices were expressed according to thefollowing tour criteria of:

    ______________________________________                                        Bactericidal index of less than 1                                                                         . . . 1                                           Bactericidal index of at least 1 to less than 2                                                           . . . 2                                           Bactericidal index of at least 2 to less than 3                                                           . . . 3                                           Bactericidal index of at least 3                                                                          . . . 4                                           ______________________________________                                    

Table 6 shows the results.

                  TABLE 6                                                         ______________________________________                                        Bactericidal Test: weight (mg/g fabric) of Test Compound Fixed                to "Antibacterial Fabric" and antibacterial effect                            ______________________________________                                                            S. aureus B. subtilis                                     Ex.    weight       FDA 209P  ATCC 6633A                                      ______________________________________                                        47     1.0 mg       3         3                                                      2.0 mg       3         3                                                      5.0 mg       4         4                                               48     1.0 mg       3         3                                                      2.1 mg       3         3                                                      5.3 mg       4         4                                               49     1.1 mg       3         3                                                      2.2 mg       3         3                                                      5.3 mg       4         4                                               ______________________________________                                                      K. pneumoniae                                                                              E. coli P. aeruginosa                              Ex.   weight  ATCC 4352    IFO 3301                                                                              ATCC 10145                                 ______________________________________                                        47    1.0 mg  3            3       3                                                2.0 mg  3            3       3                                                5.0 mg  4            4       4                                          48    1.0 mg  3            3       3                                                2.1 mg  3            3       3                                                5.3 mg  4            4       4                                          49    1.1 mg  3            3       3                                                2.2 mg  3            3       3                                                5.3 mg  4            4       4                                          ______________________________________                                    

COMPARATIVE EXAMPLE 2

4-Chloromethylstyrene was subjected to suspension polymerization in theusual manner to obtain a homopolymer (PCS-H). The polymer obtained waswashed with hot acetone to remove the unreacted monomer.

TML-C₆ (56 g) obtained in Example 3 was reacted with 53.0 g of PCS-H in850 ml of THF solvent at 65° C. for 64 hours, consequently affording96.0 g of a yellow powdery polymer (yield 88.1%).

TEST EXAMPLE 3 (ACUTE SKIN IRRITATION)

The polymer obtained in Example 23, Example 40, Example 45 orComparative Example 2 was tested for acute skin irritation according toOECD Chemicals Test Guideline 2 (edited by Foundation of ChemicalsInspection Association), 404.

A powder of the compound was applied to a small portion of the skin of arabbit and covered with a gauze patch as fixed with a tape. Four hourslater, the patch was removed, and the skin was then checked. Table 7shows the results.

In Table 7:

    ______________________________________                                        0: no erythema       0: no edema                                              1: very slight erythema                                                                            1: very slight edema                                     2: distinct erythema 2: slight edema                                          3: medium to intense erythema                                                                      3: medium edema                                          4: intense erythema  4: intense edema                                         ______________________________________                                    

                  TABLE 7                                                         ______________________________________                                                    Time after removing patch                                                     1 hour                                                                              24 hours 48 hours 72 hours                                  ______________________________________                                        Ex. 23   erythema 0       0      0      0                                              edema    0       0      0      0                                     Ex. 40   erythema 0       0      0      0                                              edema    0       0      0      0                                     Ex. 45   erythema 0       0      0      0                                              edema    0       0      0      0                                     Com. Ex. 2                                                                             erythema 2       1      0      0                                              edema    1       0      0      0                                     ______________________________________                                    

EXAMPLES 50 TO 52

A 0.5 g quantity of each of the polymers obtained in Examples 23, 40 and43 was dissolved in 100 g of methanol. A cut piece of high-densitypolyethylene film (HDPE, 80 μm in thickness), measuring 14 cm×50 cm, wasimmersed in each of the three kinds of methanol solutions for 30seconds, then withdrawn and dried at 25° C. for 1 hour, followed byfurther drying in a dryer at 50° C. for 1 hour. The film pieces thusprepared are referred to as Examples 50, 51 and 52.

The amount of polymer deposited on the film surface was 0.1 μmol/cm².

COMPARATIVE EXAMPLES 3 AND 4

Polyurethane resin (0.2 g), 30 g of methyl ethyl ketone, 70 g of tolueneand 0.2 g of benzalkonium chloride (product of NAKALAI TESQUE INC.) weremixed together to prepare a solution, in which the same HDPE film pieceas used for Example 50 was immersed, followed by the same treatment asabove to prepare Comparative Example 3.

Comparative Example 4 was prepared in the same manner as in Example 11except that the benzalkonium chloride was replaced by1,6-di(N-p-chlorophenylbiguanide)-hexanedigluconate.

TEST EXAMPLES 4 (ADHESION TO FILM)

Each of the HDPE film pieces of Examples 50 to 52 and ComparativeExamples 3 and 4 was placed into a 2-liter beaker along with 1 liter ofdistilled water, followed by vigorous stirring at 25° C. for 8 hours fora separation test. The film was withdrawn, dried at 25° C. for 1 hour,thereafter treated with 10⁻⁴ M Bromophenol Blue (phosphoric acid bufferpH 7.0) to develop a blue color over the surface and checked forseparation or release of the high polymer compound coating to determinea change in the adhesion to the film due to the separation test. Table 8shows the result.

In Table 8, a uniformly colored sample is represented by ∘, and alocally unevenly colored sample by Δ.

                  TABLE 8                                                         ______________________________________                                               before separation test                                                                     after separation test                                     ______________________________________                                        Ex. 50   ◯  ◯                                         Ex. 51   ◯  ◯                                         Ex. 52   ◯  ◯                                         Com. Ex. 3                                                                             ◯  Δ                                               Com. Ex. 4                                                                             ◯  Δ                                               ______________________________________                                    

TEST EXAMPLE 5 (ANTIBACTERIAL TEST OF FILM)

The film pieces of Examples 50 to 52 and Comparative Examples 3 and 4were partly tested for separation with saturated steam at 90° C. for 90minutes and thereafter dried at 25° C. for 24 hours for use as samplesfor the following test after the separation test.

A cell culture incubated with shaking on a nutrient broth (Difco. Lab.)for 18 hours was diluted with aseptic water to 10⁴ cells/ml. Film pieces(Examples 11 to 20, Comparative Examples 2 and 3) cut out before andafter the separation test were placed into a gas barrier bag ofpolypropylene (180×80 cm) along with 50 ml of the diluted culture, andthe bag was heat sealed. The bag containing the film pieces was set in aconstant-temperature shaking culture device at 37° C. and tested for 18hours.

After the incubation test, the resulting cell suspension was collectedand checked for the number of remaining cells by the usual colonycounting method. The following nine strains were used as test bacteria.

    ______________________________________                                        No.                                                                           ______________________________________                                        1.     Pseudomonas aeruginosa                                                                           resistant isolate                                   2.     Klebsiella pneumoniae                                                                            resistant isolate                                   3.     Escherichia coli   resistant isolate                                   4.     Staphylococcus aureus                                                                            resistant isolate a                                 5.     Staphylococcus aureus                                                                            resistant isolate b                                 6.     Staphylococcus aureus                                                                            resistant isolate c                                 7.     Staphylococcus aureus                                                                            resistant isolate d                                 8.     Staphylococcus aureus                                                                            resistant isolate e                                 9.     Bacillus subtilis  resistant isolate                                   ______________________________________                                    

Live cell counts of at least 10⁵ cells/ml are represented by X, those of10³ ˜10⁴ cells/ml by Δ, those of 10˜10² cells/ml by ∘, and zero by ⊚.Table 9 shows the results. The test strains listed in Table 9 were eachrepresented only by the corresponding number given above.

                  TABLE 9                                                         ______________________________________                                        Antibacterial test of film (number of live cells)                             before separation test                                                               Test strain No.                                                               1    2     3      4   5    6   7    8    9                             ______________________________________                                        Ex. 50   ⊚                                                                     ⊚                                                                    ⊚                                                                   ⊚                                                                  ⊚                                                                   ⊚                                                                  ⊚                                                                   ⊚                                                                   ⊚            Ex. 51   ⊚                                                                     ⊚                                                                    ⊚                                                                   ⊚                                                                  ⊚                                                                   ⊚                                                                  ⊚                                                                   ⊚                                                                   ⊚            Ex. 52   ⊚                                                                     ⊚                                                                    ⊚                                                                   ⊚                                                                  ⊚                                                                   ⊚                                                                  ⊚                                                                   ⊚                                                                   ⊚            Com. Ex. 3                                                                             ◯                                                                        ◯                                                                       ◯                                                                      ◯                                                                     ◯                                                                      ◯                                                                     ◯                                                                      ◯                                                                      ◯               Com. Ex. 4                                                                             ◯                                                                        ◯                                                                       ◯                                                                      ◯                                                                     ◯                                                                      ◯                                                                     ◯                                                                      ◯                                                                      ◯               Ex. 50   ◯                                                                        ⊚                                                                    ◯                                                                      ⊚                                                                  ⊚                                                                   ⊚                                                                  ⊚                                                                   ⊚                                                                   ⊚            Ex. 51   ◯                                                                        ⊚                                                                    ◯                                                                      ⊚                                                                  ⊚                                                                   ⊚                                                                  ⊚                                                                   ⊚                                                                   ⊚            Ex. 52   ◯                                                                        ⊚                                                                    ◯                                                                      ⊚                                                                  ⊚                                                                   ⊚                                                                  ⊚                                                                   ⊚                                                                   ⊚            Com. Ex. 3                                                                             Δ                                                                              Δ                                                                             Δ                                                                            Δ                                                                           Δ                                                                            Δ                                                                           Δ                                                                            Δ                                                                            Δ                     Com. Ex. 4                                                                             Δ                                                                              Δ                                                                             Δ                                                                            Δ                                                                           Δ                                                                            Δ                                                                           Δ                                                                            Δ                                                                            Δ                     ______________________________________                                    

EXAMPLES 53 TO 55

Each of the polymers obtained in Examples 23, 40 and 45 was made into0.5 wt. % methanol solution, in which a fabric (cotton shirting, JISstandard fabric) was immersed and treated by the exhaustion method foruse in an antibacterial test. The concentration of the polymer appliedto the fabric was so adjusted that the amount of active groups of thepolymer supported thereon would be 5 μmoles/g fabric. Thus, Examples 53,54 and 55 were prepared.

COMPARATIVE EXAMPLE 5

Benzalkonium chloride (BAG) was dissolved in a resin emulsion to aconcentration of 0.5 wt. % and then applied to the same fabric as usedfor Example 53. The fabric was dried at 50° C. for 12 hours andthereafter subjected to an antibacterial test. The concentration of BAGapplied to the fabric was adjusted to 5 μmoles/g fabric.

TEST EXAMPLE 6 (ANTIBACTERIAL TEST OF FABRIC)

Each of the fabrics of Examples 53 to 55 and Comparative Example 5 wassubjected to a bacterial growth inhibition test to calculate thesterilization efficiency, without laundering or after having beenlaundered a specified number of times.

In each of the laundering cycles, the fabric was laundered at a watertemperature of 40° C. in a bath ratio of 1:30 for 5 minutes using ahousehold electric washing machine and "NISSAN NONION NS-210" (productof Nippon Oils & Fats Co., Ltd.) as a detergent in an amount of 0.5 gper liter of water, and thereafter washed with water for 5 minutes whileallowing water to overflow the machine.

The bacterial growth inhibition test was conducted by the followingmethod using the same nine strains as in Test Example 4 as testbacteria. According to a JIS test method (to be incorporated into JIS in1993), the test fabric (0.2 g) was placed into aseptic bile andautoclaved at 121° C. for 15 minutes for sterilization. The strain wasincubated with shaking on NB medium at 37° C. for 18 hours, and theculture was diluted with 1/1NB to about 10⁶ cells/ml. The bile wasinoculated with 0.1 ml oi the cell suspension, followed by incubation at37° C. for 18 hours. After the incubation, 10 ml of physiological salinecontaining 0.2% Tween 80 was added to the bile, and the mixture wasshaken to wash out the resulting cells. The number of live cells wasdetermined by the usual colony counting method. The test result isexpressed in the same manner as in Test Example 4. Table 10 shows theresult.

                  TABLE 10                                                        ______________________________________                                        Antibacterial test of fabric (number of live cells)                                  Test strain No.                                                               1    2     3      4   5    6   7    8    9                             ______________________________________                                               Laundering 0 cycle                                                     Ex. 53   ◯                                                                        ⊚                                                                    ◯                                                                      ⊚                                                                  ⊚                                                                   ⊚                                                                  ⊚                                                                   ⊚                                                                   ⊚            Ex. 54   ⊚                                                                     ⊚                                                                    ⊚                                                                   ⊚                                                                  ⊚                                                                   ⊚                                                                  ⊚                                                                   ⊚                                                                   ⊚            Ex. 55   ⊚                                                                     ⊚                                                                    ⊚                                                                   ⊚                                                                  ⊚                                                                   ⊚                                                                  ⊚                                                                   ⊚                                                                   ⊚            Com. Ex. 5                                                                             ◯                                                                        ◯                                                                       ◯                                                                      ◯                                                                     ◯                                                                      ◯                                                                     ◯                                                                      ◯                                                                      ◯                      Laundering 10 cycles                                                   Ex. 53   ◯                                                                        ⊚                                                                    ◯                                                                      ⊚                                                                  ⊚                                                                   ⊚                                                                  ⊚                                                                   ⊚                                                                   ⊚            Ex. 54   ⊚                                                                     ⊚                                                                    ⊚                                                                   ⊚                                                                  ⊚                                                                   ⊚                                                                  ⊚                                                                   ⊚                                                                   ⊚            Ex. 55   ⊚                                                                     ⊚                                                                    ⊚                                                                   ⊚                                                                  ⊚                                                                   ⊚                                                                  ⊚                                                                   ⊚                                                                   ⊚            Com. Ex. 5                                                                             X      X     X    X   X    X   X    X    X                           ______________________________________                                    

(Industrial applicability)

The present invention provides a polymerizable monomer for readilygiving an antibacterial polymer which is excellent in bactericidalactivity, high in safety and stability and capable of retaining itseffect for a prolonged period of time even in a reactive environment,and provides the polymer thereof.

We claim:
 1. A polymerizable monomer represented by the general formula(1) ##STR63## wherein R¹ is a hydrogen atom, methyl, chlorine or cyano,R² is alkylene having 1 to 4 carbon atoms, R³ is alkylene having 3 to 10carbon atoms, R⁴ is alkyl having 6 to 18 carbon atoms, R⁵ to R⁸ are thesame or different and are each alkyl or substituted alkyl having 1 to 3carbon atoms, A is methylene, phenylene, substituted phenylene, --CH₂O--, --CH₂ CH₂ O--, --CO--, --CO--N(R⁹)-- (wherein R⁹ is a hydrogen atomor methyl) or vinylene, m is 0 or 1, and X and Y are the same ordifferent, and are each a monovalent anion or form a bivalent anion whentaken together.
 2. A polymer which has a structural unit derived fromnoncrosslinkable or crosslinkable vinyl monomer or from a mixture ofsuch monomers, and a structural unit represented by the general formula(2) ##STR64## wherein R¹ is a hydrogen atom, methyl, chlorine or cyano,R² is alkylene having 1 to 4 carbon atoms, R³ is alkylene having 3 to 10carbon atoms, R⁴ is alkyl having 6 to 18 carbon atoms, R⁵ to R⁶ are thesame or different and are each alkyl or substituted alkyl having to 1 to3 carbon atoms, A' is methylene, --CH₂ O--, --CH₂ CH₂ O--, --CO--,--CO--N(R⁹)-- (wherein R⁹ is a hydrogen atom or methyl) or vinylene, mis 0 or 1, and X and Y are the same or different, and are each amonovalent anion or form a bivalent anion when taken together.
 3. Aprocess for preparing a polymer characterized by polymerizing anoncrosslinkable or crosslinkable vinyl monomer or a mixture of suchmonomers with a monomer represented by the general formula (1).
 4. Adisinfectant composition comprising a polymer for destroying bacteriawhich are resistant to antibiotics, said polymer having a structuralunit derived from the general formula (2) ##STR65## wherein R¹ is ahydrogen atom, methyl, chlorine or cyano, R² is alkylene having 1 to 4carbon atoms, R³ is alkylene having 3 to 10 carbon atoms, R⁴ is alkylhaving 6 to 18 carbon atoms, R⁵ to R⁸ are the same or different and areeach alkyl or substituted alkyl having 1 to 3 carbon atoms, A' ismethylene, --CH₂ O--, --CH₂ CH₂ O--, --CO--, --CO--N(R⁹)-- or vinylene,R⁹ is a hydrogen atom or methyl, m is 0 or 1, and X and Y are the sameor different, and are each a monovalent anion or form a bivalent anionwhen taken together.
 5. A method of imparting antibacterial propertiesto fibers by applying to the fibers, a polymer having a structural unitderived from the general formula (2) ##STR66## wherein R¹ is a hydrogenatom methyl, chlorine or cyano, R² is alkylene having 1 to 4 carbonatoms, R³ is alkylene having 3 to 10 carbon atoms, r⁴ is alkyl having 6to 18 carbon atoms, R⁵ to R⁸ are the same or different and are eachalkyl or substituted alkyl having 1 to 3 carbon atoms, A' is methylene,--CH₂ O--, --CH₂ CH₂ O--, --CO--, --CO--N(R⁹)-- or vinylene, R⁹ is ahydrogen atom or methyl, m is 0 or 1, and X and Y are the same ordifferent, and are each a monovalent anion or form a bivalent anion whentaken together.